Formation of unusual Cr5+ charge state in CaCr0.5Fe0.5O3 perovskite

doi:10.1088/1674-1056/27/3/037503

Abstract

A new oxide CaCr_0.5Fe_0.5O₃ was prepared under high pressure and temperature conditions. It crystallizes in a B-site disordered Pbnm perovskite structure. The charge combination is determined to be Cr⁵⁺/Fe³⁺ with the presence of unusual Cr⁵⁺ state in octahedral coordination, although Cr⁴⁺ and Fe⁴⁺ occur in the related perovskites CaCrO₃ and CaFeO₃. The randomly distributed Cr⁵⁺ and Fe³⁺ spins lead to short-range ferromagnetic coupling, whereas an antiferromagnetic phase transition takes place near 50 K due to the Fe³⁺-O-Fe³⁺ interaction. In spite of the B-site Cr⁵⁺/Fe³⁺ disorder, the compound exhibits electrical insulating behavior. First-principles calculations further demonstrate the formation of CaCr_0.5⁵⁺Fe_0.5³⁺O₃ charge combination, and the electron correlation effect of Fe³⁺ plays an important role for the insulting ground state. CaCr_0.5Fe_0.5O₃ provides the first Cr⁵⁺ perovskite system with octahedral coordination, opening a new avenue to explore novel transition-metal oxides with exotic charge states.

Keywords: high pressure synthesis perovskite valence state

Received: 30 January 2018
Revised: 09 February 2018
Accepted manuscript online:

PACS:	75.10.-b	(General theory and models of magnetic ordering)
	61.05.cj	(X-ray absorption spectroscopy: EXAFS, NEXAFS, XANES, etc.)
	71.45.Gm	(Exchange, correlation, dielectric and magnetic response functions, plasmons)
	62.50.-p	(High-pressure effects in solids and liquids)

Fund:

Project supported by the National Natural Science Foundation of China (Grant Nos. 11574378, 51772324, and 61404052), the National Basic Research Program of China (Grant No. 2014CB921500), and the Chinese Academy of Sciences (Grant Nos. YZ201555, QYZDB-SSW-SLH013, GJHZ1773, and XDB07030300).

Corresponding Authors: Yi-feng Yang, You-Wen Long
E-mail: yifeng@iphy.ac.cn;ywlong@iphy.ac.cn

Cite this article:

Jian-Hong Dai(戴建洪), Qing Zhao(赵庆), Qian Sun(孙倩), Shuo Zhang(张硕), Xiao Wang(王潇), Xu-Dong Shen(申旭东), Zhe-Hong Liu(刘哲宏), Xi Shen(沈希), Ri-Cheng Yu(禹日成), Ting-Shan Chan(詹丁山), Lun-Xiong Li(李论雄), Guang-Hui Zhou(周光辉), Yi-feng Yang(杨义峰), Chang-Qing Jin(靳常青), You-Wen Long(龙有文) Formation of unusual Cr⁵⁺ charge state in CaCr_0.5Fe_0.5O₃ perovskite 2018 Chin. Phys. B 27 037503

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Formation of unusual Cr5+ charge state in CaCr0.5Fe0.5O3 perovskite

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Formation of unusual Cr⁵⁺ charge state in CaCr_0.5Fe_0.5O₃ perovskite